THERMAL, CHEMICAL AND THERMOELECTRIC EFFECT

Joules Law:
Q = I2 R t Q= I2 R t J
Q is in Joule, I in Amp, R in ohm and t in sec. Q is in Calorie, I in Amp, R in ohm and t in sec.

Electric Power:
P=VI P = I2 R P = V2 / R SI unit of power is watt. Other units are kW and hp. 1 kW = 1000 W 1 hp = 746 W

Electric Energy:
E=VIt E = I2 R t E = V2 t / R Commercial Unit of Electric Energy is kWh or B.O.T.U. 1 kWh = 3.6 x 106 Joule

Electric Fuse:
Fuse is generally made of alloy of 63% tin and 37% lead. It has high resistance and low melting point.

Electric Heating Appliances use Nichrome wire (alloy of Ni and Cr). It is used because: i) It has high specific resistance ii) It has high melting point iii) It has high malleability iv) It is not easily oxidised. For given V, PI P1/R

i.e. i) Higher the power of the appliance, more is the current drawn ii) Higher the power of the appliance, less is the resistance.

Maximum Power Theorem:

I= E R+r P = I2 R I E E r v R V =0 Maximum Power = E2 4R I

Output power of source of emf, R+r For output power to be maximum, Manipulating, we get R=r P=[ ] R
2

dP dR

Faradays Laws of Electrolysis:

I Law:
The mass of the ions liberated at the anode or deposited at the cathode in electrolysis is directly proportional to the quantity of electricity, i.e. charge passed through the electrolyte. If m be the mass of the ions and q the total charge passed, then mq or m=zq or m=zIt

II Law:

where z is called electrochemical equivalent (e.c.e) of the substance.

When the same electric current is passed through several electrolytes for the same time, the masses of the various ions deposited at the respective cathodes or liberated at the respective anodes are proportional to their chemical equivalents. mA EA m = E
B B

Relation between z, E, M, p, F, etc.:

zA zB = EA EB M p or F= Eq m

z E z

=F

Faraday (F) is the quantity of charge required to liberate one gram equivalent of a substance during electrolysis. It may also be defined as the charge required to liberate one mole of a monovalent element during electrolysis. F = 96500 C / mol.

Daniel cell:

Action at Zn Anode:
Zn dissociates and Zn ions pass into the solution. Zn Zn++ + 2 eH2 SO4 2H+ + SO4-Zn++ + SO4-- Zn SO4 Zn + H2SO4 Zn SO4 + 2H + 2e
+ -

Cu SO4 Crystals Porous Pot Zn SO4 Solution Zinc Rod Cu SO4 Solution Copper Vessel

The hydrogen ions so formed diffuse through the porous pot and act on the copper sulphate forming sulphuric acid and liberating Cu++ ions. 2H+ + Cu SO4 H2 SO4 + Cu++

Action at Cu Cathode:
These positive ions are deposited on the copper plate, thereby making copper plate positive with respect the electrolyte. So, there is no polarisation. Thus, Cu SO4 acts as depolariser. The EMF of Daniel cell is 1.12 volt.

Leclanche cell:
Action at Zn Anode:
Zn dissociates and Zn ions pass into the solution. Zn Zn++ + 2 e2NH4 Cl 2NH3 + 2H+ + 2ClZn++ + 2Cl- Zn Cl2 Zn + 2NH4 Cl 2NH3 + Zn Cl2 + 2H+ + 2eThe ammonium gas escapes. The hydrogen ions diffuse through the pores of the porous pot. Hydrogen ions react with manganese dioxide. 2H+ + 2Mn O2 Mn2 O3 + H2O + 2e+
Porous Pot Mn O2 and Charcoal Powder Carbon Rod Amalgamated Zinc Rod NH4 Cl Solution Glass Vessel

Action at Carbon Cathode:

These positive charges are transferred to the carbon rod. So, the carbon rod becomes positive with respect to the electrolyte. When the cell is allowed to rest for some time by keeping the porous pot outside the cell, Mn2 O3 is once again converted into Mn O2 2Mn2 O3 + O2 4 Mn O2 EMF of Leclanche cell is 1.5 volt.

Lead Acid Cell:

Discharging:

Secondary Cells:
Vent Plug

When the cell is connected to an external resistance, current begins to flow. The sulphuric acid dissociates into hydrogen (H+)and sulphate (SO4-- ) ions. The hydrogen ions move towards the positive plate. The sulphate ions move towards the negative plate. While delivering charges to the plates, the ions convert the active materials of each to lead sulphate.

Pb

Pb

Pb O2

Pb O2 Dilute H2 SO4

Action at the negative plate (Pb):

Pb + SO4-- - 2 e PbSO4 PbO + H2O PbSO4 + H2O

Action at the positive plate (PbO2):

PbO2 + 2H+ + 2 ePbO + H2SO4

PbO2 + H2SO4 + 2H+ + 2 e- PbSO4 + 2 H2O But H2SO4 molecules do not exist in the solution. These are dissociated into 2H+ and SO4-- ions. So, the net reaction at the positive plate is: PbO2 + SO4-- + 4H+ + 2 e PbSO4 + 2H2O The lead sulphate produced in these reactions is a soft form. It is chemically more active than the hard lead. When the emf of cell falls 1.9 V, it requires to be charged.

Charging:
When the cell is to be charged, it is connected in opposition to a supply of greater emf. The hydrogen ions are carried to the negative plate and sulphate ions to the positive plate.

Action at the negative plate (Pb):

PbSO4-- + 2 H+ + 2e- Pb + H2SO4

Action at the positive plate (PbO2):

PbSO4 + SO4 -- - 2 e2SO3 + 2H2O 2H2SO4

PbO2 + 2SO3 EMF of freshly prepared cell is 2.2 volt.

PbSO4 + 2H2O + SO4-- - 2 e- PbO2 + 2 H2 SO4

Seebeck Effect:
E = t + t2
where and are thermoelectric constants The current produced in this effect is called thermoelectric current and the emf is called thermoelectric emf. Thermoelectric emf is usually in the order of V. Hot Fe

Cu Fe Cold

Hot CofFee

Seebeck Series (Cold Junction):

The magnitude and direction of thermo emf in a thermocouple depends not only on the temperature difference between the hot and cold junctions but also on the nature of metals constituting the thermocouple.

Sb, As, Fe, Cd, Zn, Ag, Au, Mo, Sn, Pb, Hg, Mn, Cu, Pt, Co, Ni, Bi
The magnitude of thermo emf in a thermocouple depends on the extent of separation of the metals in the series. The thermoelectric current flows from a metal earlier in the series to a metal later in the series across the cold junction. Note: For hot junction, just reverse the series.

Variation of Seebeck EMF with Temperature:

Neutral Temperature:
T he r m o e m f
tc tn ti th The temperature of the hot junction at which the thermo emf becomes maximum is called the neutral temperature. It is independent of the temperature of the cold junction. It depends only upon the nature of the metals forming the thermocouple.

Temperature of Inversion:

The temperature of the hot junction at which the thermo emf becomes zero and then changes direction is called the temperature of inversion. It depends on the temperature of the cold junction. It also depends on the nature of the metals forming the thermocouple. ti tn = tn - tc or tn = ( ti + tc ) / 2

Thermoelectric Power (S):

The rate of change of thermoelectric emf with temperature is called thermoelectric power. It is also known as Seebeck coefficient. E = t + t2 dE Thermoelectric power = dt S= d dt ( t + t2 ) dE dt 0 tn ti th

S= +t The graph between Seebeck power and temperature is a straight line and is called thermoelectric power line. When t = tn , dE dt =0 or or S = + tn = 0 tn =

Laws of Thermoelectricity:
1. Law of successive temperatures: For a given thermocouple, the emf for any specified temperature difference is equal to the sum of the emfs corresponding to any smaller intervals into which the given range of temperature may be sub-divided. E = 2.
tn t1

E +

t2 t1

E +

t3 t2

t4 t3

+.+ E

tn tn -1

Law of successive metals: The insertion of an additional metal or metals into any thermoelectric circuit does not change the effective emf of the circuit, provided that both the ends of each such conductor are at the same temperature. E +
D C

G A

= E

B A

+ E

C B

+.

G F

End of Thermal, Chemical and Thermoelectric Effect